EP0971590B1 - Solid mixtures based sulfonylurea and adjuvants - Google Patents

Solid mixtures based sulfonylurea and adjuvants Download PDF

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EP0971590B1
EP0971590B1 EP98922619A EP98922619A EP0971590B1 EP 0971590 B1 EP0971590 B1 EP 0971590B1 EP 98922619 A EP98922619 A EP 98922619A EP 98922619 A EP98922619 A EP 98922619A EP 0971590 B1 EP0971590 B1 EP 0971590B1
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alkyl
methyl
alkoxy
halogen
ethyl
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French (fr)
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EP0971590A1 (en
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Matthias Bratz
Karl-Friedrich Jäger
Rainer Berghaus
Hans Ziegler
Thomas Kröhl
Adolf Parg
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BASF SE
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BASF SE
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention relates to solid mixtures based on of sulfonylureas and adjuvants.
  • Sulfonylureas (hereinafter referred to as "SU") are one Group of highly active herbicides that are used in wide areas of the Crop protection application.
  • suitable wetting agents include Oil adjuvants (Nalejewa et al., Weed Technol. 1995, 9, pp. 689-695) or Alcohol ethoxylates (see above and Dunne et al., Weed Science 1994, 42, pp. 82-85; Green, Weed Technol. 1993, 7, pp. 633-640) as special appropriately described. These substances are used in agriculture Practice as a tank mix additive from the farmer Spray liquor added. The mixture of SU herbicide and surfactant only shortly before use in Spray tank made.
  • a double pack with the trade name CATO® Du Pont de Nemours
  • CATO® Du Pont de Nemours
  • component A a 25% water-dispersible granules of the active ingredient rimsulfuron
  • component B a separately packaged wetting agent
  • component B a mixture of 2-butoxyethanol, polyethoxylated Tallowamin and Nonylphenylpolyethylenglykolether exists.
  • JP-A 62/084004 describes the use of calcium carbonate and Sodium tripolyphosphate for stabilizing SU-containing formulations described.
  • JP-A 63/023806 describes problem solving through use special carriers and vegetable oils for the production of solid Formulations containing SU.
  • JP-A 08/104603 describes similar ones Effects when using epoxidized natural oils. Both of the above applications have in common Characteristic of the incorporation of vegetable oils in the solid formulation, in addition to improved stability, the effect-enhancing To use the effects of these substances, which act as adjuvants.
  • EP-367 887 and EP-A-272 542 disclose herbicides Active ingredient concentrates containing polypropylene glycol-polyethylene copolymers or a fatty alcohol ethoxylate.
  • the object of the present invention was therefore to provide solid formulations with sulfonylureas as active ingredients to provide the adjuvants already in the solid formulation and previously known solid formulations are superior.
  • alkyl ethers of copolymers of C 2 -C 4 -alkylene oxides are used as wetting agents in SU-containing solid formulations, there is a pronounced stabilization of the active compound in comparison to other wetting agents.
  • This effect is particularly surprising because structurally related compounds such as fatty alcohol ethoxylates (see Comparative Examples 1 and 2) and ethylene oxide / propylene oxide block copolymers do not show this behavior but, in contrast, even lead to a breakdown of the active ingredient.
  • the advantageous effect can be observed especially when, in addition to herbicidal active ingredients, water-soluble inorganic salts such as ammonium sulfate are present.
  • the stabilization becomes particularly clear when the wetting agent is used in the concentration required for the biological effect.
  • alkyl ethers of copolymers of C 2 -C 4 alkylene oxides and ammonium sulfate By mixing the SU with other active ingredients, alkyl ethers of copolymers of C 2 -C 4 alkylene oxides and ammonium sulfate, ready-to-use formulations with good biological effects can be obtained.
  • processes for the preparation of the invention found solid mixtures and their use as crop protection agents to combat unwanted harmful plants.
  • SUs with their INN International Nonproprietary Name
  • ACC 322140 amidosulfuron; Azimsulfuron (N - [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] -1-methyl-4- (2-methyl-2H-tetrazol-5-yl) -1H-pyrazole-5-sulfonamide ); Bensulfuron-methyl (methyl 2 - [[[[((4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] benzoate); Ethyl 2 - [[[[(4-chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate (chlorimuron ethyl); 2-chloro-N - [[(4-methoxy-6-methyl-1,3,5-triazin-2-
  • the solid formulations according to the invention contain one or more alkyl ethers of copolymers of C 2 -C 4 -alkylene oxides, preferably of statistical or block copolymers of ethylene oxide and propylene oxide.
  • the alkyl group in the ether radical generally has 10 to 25, preferably 12 to 20, carbon atoms and is preferably linear.
  • the molar ratio of ethylene oxide to propylene oxide units is not particularly limited and is usually in the range from 1:10 to 10: 1, preferably from 1: 5 to 5: 1 and in particular from 1: 3 to 3: 1.
  • the block length is generally in the range of 2-100 units per block.
  • Suitable commercially available products are, for example Antarox® BO (Rhone Poulenc), Emulsogen® V2436 (Hoechst), Dehypon® LS and LT (Henkel), Synperionic® LF (ICI Specialty Chemicals) and in particular the products of Plurafac® LF BASF Aktiengesellschaft series.
  • the proportion of component a) in the solid according to the invention Mixtures generally range from 0.5 to 75 % By weight, preferably from 1 to 25% by weight, based on the total weight the wording.
  • the proportion of component b) is generally in the range from 1 to 75, in particular 1 to 50 and particularly preferably 5 to 25 % By weight, based on the total weight of the formulation.
  • Preferred further active ingredients c) are, for example bromobutide, dimethenamide, isoxaben, propanil, glufosinate-ammonium, glyphosate, sulfosate, mefenacet, thiafluamide, 2,4-D, 2,4-DB, dichlorprop, dichlorprop-P, dichlorprop-P (2,4-DP-P), fluoroxopyr, MCPA, mecoprop, mecoprop-P, dicamba, bentazone, clomazone, diflufenican, sulcotrione, isoxaflutole, phenmedipham, thiobencarb, quinclorac, quinmerac, acetochlor, alachlor, butachlor, metazachlor, metolachlor, pretilachlor, butroxydim, caloxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, 2-
  • the proportion of other active ingredients c), if any are generally in the range of 0.5 to 75, preferably from 1 to 60% by weight of the formulation.
  • Ammonium salts of aromatic sulfonic acids e.g. Lignin--, Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as from Fatty acids of aryl sulfonates, of alkyl ethers, of lauryl ethers, of fatty alcohol sulfates and of fatty alcohol glycol ether sulfates, Condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, Condensation products of phenol or phenolsulfonic acid with Formaldehyde, condensation products of phenol with formaldehyde and sodium sulfite, polyoxyethylene octylphenol ether, ethoxylated Isoo
  • surface-active substances are used, their share is in generally in the range from 0.5 to 25% by weight, based on the total weight the solid mixture.
  • Binders such as:
  • Polyvinyl pyrrolidone polyvinyl alcohol, partially hydrolyzed Polyvinyl acetate carboxymethyl cellulose, starch, vinyl pyrrolidone / vinyl acetate copolymers and polyvinyl acetate or mixtures thereof;
  • Lubricants such as:
  • Defoamers such as:
  • Silicone emulsions long-chain alcohols, phosphoric acid esters, acetylenediols, fatty acids or organofluorine compounds, and
  • Salts of ethylenediaminetetraacetic acid EDTA
  • salts of trinitrilotriacetic acid or salts of polyphosphoric acids or their Mixtures.
  • the solid mixtures according to the invention can be in the form of powder, Granules, briquettes, tablets and similar formulation variants getting produced.
  • the powders can be water-soluble or water-dispersible powders.
  • With the granules can be water-soluble or water-dispersible granules for use in spray application or around so-called scatter granules act for direct application.
  • the average particle size the granules are generally between 200 microns and 2 mm.
  • the granule formulations obtained are dust-free, free-flowing, non-caking products that are readily soluble in cold water or are dispersible.
  • the products can easily be larger Quantities are filled.
  • containers such as plastic, paper, Laminate bags or pouches can be found in boxes or other Bulk containers are handled.
  • water-soluble foil bags e.g. Polyvinyl alcohol film pouches
  • water-soluble films can be used i.a. Polyvinyl alcohol or cellulose derivatives such as methyl cellulose, methyl hydroxypropyl cellulose or Carboxymethylcellulose.
  • the water soluble bags are in one water vapor impermeable outer shell such as polyethylene film, packed in polyethylene-laminated paper or aluminum foil.
  • solid formulations according to the invention can be produce various methods known to those skilled in the art.
  • extruder granulation As a preferred manufacturing process for the formulations mentioned are extruder granulation, spray drying, fluid bed agglomeration, Mixer granulation and plate granulation.
  • Fluidized bed granulation is particularly suitable. ever according to the desired composition of the formulation aqueous solution, emulsion or suspension, all of which are components of the formulation contains, sprayed and agglomerated in a WSG apparatus.
  • active ingredient salts and / or inorganic Ammonium salts are presented in the apparatus and with a Solution or emulsion / suspension of the remaining ingredients of the formulation sprayed and agglomerated.
  • aqueous solutions, emulsions or suspensions that contain certain recipe components, one after the other Active ingredient granules, an active ingredient salt and / or an inorganic Apply ammonium salt and so different enveloping layers to obtain.
  • extruder granulation are preferably suitable for extruder granulation Basket, radial or dome extruder with low compression of the Granule.
  • solid mixtures serve mixtures of active ingredients, formulation aids and possibly water-soluble salts. These are generally pre-ground. Sometimes it is sufficient if only the water-insoluble ones Materials are pre-ground in suitable mills.
  • Water the ones according to the invention, are suitable as the granulating liquid Alkyl ethers of alkylene oxides or aqueous solutions thereof.
  • Aqueous solutions from anorg are also suitable.
  • binders such as polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, Starch, vinyl pyrrolidine / vinyl acetate copolymers, Sugar, dextrin or polyethylene glycol.
  • a premix consisting of: 225 g distilled water 13 g SU 1 (technical 95.7%) 13 g Tamol® NH 26 g Ufoxane® 3A 2.1 g Antifoam emulsion SRE 37.5 g Extrusil® 62.5 g Wettol® LF 700 was mixed and ground in a bead mill. The resulting suspension was later used as a spray mixture.
  • SU-1 Verb. 47 from Table 1 clefoxydim 2- ⁇ 1- [2- (4-chlorophenoxy) -propyloxyamino] -butyl ⁇ -5-tetrahydrothiopyran-3-yl-cyclohexane-1,3-dione Cinidon-ethyl Ethyl (Z) -2-chloro-3- [2-chloro-5- (4,5,6,7-tetrahydro-1,3-dioxoisoindoldion-2-yl -) - phenyl) acrylate
  • the active ingredient content of SU of the formulations according to the above Examples were determined using quantitative HPLC, and is given in Table 3 in percent.
  • Table 3 shows the results from the determination of the storage stability of the solid mixtures prepared from Example 1 and Comparative Examples 1-3.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to solid mixtures containing: a) an active substance from the sulfonylurea group and b) an alkyl ether obtained from copolymers of C2-C4-alkylene oxides.

Description

Die vorliegende Erfindung betrifft feste Mischungen auf der Basis von Sulfonylharnstoffen und Adjuvantien.The present invention relates to solid mixtures based on of sulfonylureas and adjuvants.

Sulfonylharnstoffe (im folgenden mit "SU" bezeichnet) sind eine Gruppe von hochaktiven Herbiziden, die in weiten Bereichen des Pflanzenschutzes Anwendung finden.Sulfonylureas (hereinafter referred to as "SU") are one Group of highly active herbicides that are used in wide areas of the Crop protection application.

Bedingt durch den Mechanismus der Wirkstoffaufnahme über das Blatt kann die Wirkung von SU durch Zusatz oberflächenaktiver Stoffe wie Netzmittel zur Spritzbrühe verbessert werden (vgl. Green et al.,ANPP, Seizieme conference du columa - Journees internationales sur la lutte contre les mauvaises herbes 1995, S. 469-474; "DPX-KG 691 - A new surfactant for sulfonyl urea herbicides").Due to the mechanism of drug absorption via the Leaf can have the effect of SU by adding surfactant Substances such as wetting agents for spray liquors are improved (cf. Green et al., ANPP, Seizieme conference du columa - Journees internationales sur la lutte contre les mauvaises herbes 1995, Pp. 469-474; "DPX-KG 691 - A new surfactant for sulfonyl urea herbicides").

In der Literatur werden als geeignete Netzmittel u.a. Öl-Adjuvantien (Nalejewa et al., Weed Technol. 1995, 9, S. 689-695) oder Alkoholethoxylate (s.o. sowie Dunne et al., Weed Science 1994, 42, S. 82-85; Green, Weed Technol. 1993, 7, S. 633-640) als besonders geeignet beschrieben. Diese Stoffe werden in der landwirtschaftlichen Praxis als Tank-Mix-Additive vom Landwirt der Spritzbrühe zugesetzt. Dabei wird die Mischung aus SU-Herbizid und oberflächenaktivem Stoff erst kurz vor der Anwendung im Spritztank hergestellt.In the literature, suitable wetting agents include Oil adjuvants (Nalejewa et al., Weed Technol. 1995, 9, pp. 689-695) or Alcohol ethoxylates (see above and Dunne et al., Weed Science 1994, 42, pp. 82-85; Green, Weed Technol. 1993, 7, pp. 633-640) as special appropriately described. These substances are used in agriculture Practice as a tank mix additive from the farmer Spray liquor added. The mixture of SU herbicide and surfactant only shortly before use in Spray tank made.

Kommerziell erhältlich ist z.B. ein Doppelpack mit dem Handelsnamen CATO® (Du Pont de Nemours), welcher aus einem 25 %igen wasserdispergierbaren Granulat des Wirkstoffs Rimsulfuron (Komponente A) und einem separat abgepackten Netzmittel (Komponente B) bestehend aus einer Mischung aus 2-Butoxyethanol, polyethoxyliertem Tallowamin und Nonylphenylpolyethylenglykolether besteht. Zur Anwendung werden beide Komponenten wie oben beschrieben im Spritztank gemischt.Commercially available is e.g. a double pack with the trade name CATO® (Du Pont de Nemours), which consists of a 25% water-dispersible granules of the active ingredient rimsulfuron (component A) and a separately packaged wetting agent (component B) consisting of a mixture of 2-butoxyethanol, polyethoxylated Tallowamin and Nonylphenylpolyethylenglykolether exists. to Both components are used as described above in the application Spray tank mixed.

in der Praxis wäre es wünschenswert. Fertigformulierungen einsetzen zu können, in denen ein wirkungssteigerndes Netzmittel bereits enthalten ist, um die problematische Mischung unmittelbar vor der Anwendung zu vermeiden. Auf diese Weise könnten logistische Probleme und Mischungsfehler beim Ansetzen der Spritzbrühe vermieden werden. Ferner sind Festformulierungen generell aus anwendungstechnischer Sicht bei der Gestaltung und Entsorgung der Verpackungen vorteilhaft.in practice it would be desirable. Use ready formulations to be able to use an effective wetting agent is included to the problematic mix immediately to avoid before application. This could be logistical Problems and mixing errors when preparing the spray mixture be avoided. Furthermore, solid formulations are generally from application technology View in the design and disposal of the Packaging advantageous.

Aus der Literatur ist weiterhin bekannt, daß Formulierungen, die Sulfonylharnstoffe enthalten, bezüglich der Stabilität der Wirkstoffe problematisch sind, da der Wirkstoff sich unter ungünstigen Bedingungen im Lauf der Zeit zersetzen kann. Die gewünschte herbizide Wirkung ist dann nicht mehr gegeben. Die Tendenz zur Zersetzung ist auch hinsichtlich der Registrierungsanforderungen problematisch, da bei der Registrierung bestimmte Mindestanforderungen an die Stabilität von PS-Wirkstoffen in Formulierungen gestellt werden.It is also known from the literature that formulations which Contain sulfonylureas with regard to the stability of the active ingredients are problematic because the active ingredient is among unfavorable Conditions can degrade over time. The desired Herbicidal activity is then no longer present. The tendency to Decomposition is also regarding the registration requirements problematic because certain minimum requirements for registration to the stability of PS active ingredients in formulations become.

In der JP-A 62/084004 wird die Verwendung von Calciumcarbonat und Natrium-tripolyphosphat zur Stabilisierung von SU-haltigen Formulierungen beschrieben.JP-A 62/084004 describes the use of calcium carbonate and Sodium tripolyphosphate for stabilizing SU-containing formulations described.

Die JP-A 63/023806 beschreibt eine Problemlösung durch Verwendung spezieller Trägerstoffe und Pflanzenöle zur Herstellung fester SU-haltiger Formulierungen. Die JP-A 08/104603 beschreibt ähnliche Effekte bei der Verwendung von epoxydierten natürlichen Ölen. Beide vorstehend genannten Anmeldungen haben als gemeinsames Merkmal die Inkorporation von Pflanzenölen in der Festformulierung, um neben einer verbesserten Stabilität die wirkungssteigernden Effekte dieser als Adjuvantien wirksamen Stoffe zu nutzen.JP-A 63/023806 describes problem solving through use special carriers and vegetable oils for the production of solid Formulations containing SU. JP-A 08/104603 describes similar ones Effects when using epoxidized natural oils. Both of the above applications have in common Characteristic of the incorporation of vegetable oils in the solid formulation, in addition to improved stability, the effect-enhancing To use the effects of these substances, which act as adjuvants.

Bei der Einarbeitung von Pflanzenölen in flüssige Formulierungen (in der Regel Suspensionskonzentrate) werden ähnliche Effekte ausgenutzt (vgl. EP-A 313317 und EP-A 554015).When incorporating vegetable oils into liquid formulations (usually suspension concentrates) have similar effects exploited (see. EP-A 313317 and EP-A 554015).

EP-367 887 und EP-A-272 542 offenbaren herbizide Wirkstoffkonzentrate, enthaltend Polypropylenglykol-polyäthylen-Copolymere oder ein Fettalkoholethoxylate.EP-367 887 and EP-A-272 542 disclose herbicides Active ingredient concentrates containing polypropylene glycol-polyethylene copolymers or a fatty alcohol ethoxylate.

Aus dem Stand der Technik ist auch bekannt, daß Alkoholalkoxylate zusammen mit Sulfonylharnstoffen als Tank-Mix-Additive eingesetzt werden können.It is also known from the prior art that alcohol alkoxylates used together with sulfonylureas as tank mix additives can be.

Aufgabe der vorliegenden Erfindung war es daher, Festformulierungen mit Sulfonylharnstoffen als Wirkstoffen zur Verfügung zu stellen, die Adjuvantien bereits in der Festformulierung enthalten und bisher bekannten Festformulierungen überlegen sind.The object of the present invention was therefore to provide solid formulations with sulfonylureas as active ingredients to provide the adjuvants already in the solid formulation and previously known solid formulations are superior.

Diese Aufgabe wird erfindungsgemäß durch feste Mischungen gelöst, die enthalten

  • a) einen Sulfonylharnstoff und
  • b) ein Adjuvant aus der Gruppe der Alkylether von Copolymeren von C2-C4-Alkylenoxiden.
    • This object is achieved according to the invention by solid mixtures which contain
  • a) a sulfonylurea and
  • b) an adjuvant from the group of alkyl ethers of copolymers of C 2 -C 4 alkylene oxides.

    • überraschenderweise wurde gefunden, daß bei Verwendung von Alkylethern von Copolymeren von C2-C4-Alkylenoxiden als Netzmittel in SU-haltigen Feststoffformulierungen eine ausgeprägte Stabilisierung des Wirkstoffs im Vergleich zu anderen Netzmitteln auftritt.
    Dieser Effekt ist besonders überraschend, weil strukturell verwandte Verbindungen wie Fettalkoholethoxylate (siehe Vergleichsbeispiele 1 und 2) und Ethylenoxid/Propylenoxid-Blockcopolymere dieses Verhalten nicht zeigen, sondern im Gegensatz sogar zu einem Abbau des Wirkstoffs führen. Der vorteilhaft Effekt ist vor allem dann zu beobachten, wenn neben herbiziden Wirkstoffen wasserlösliche anorganische Salze wie Ammoniumsulfat vorhanden sind. Besonders deutlich wird die Stabilisierung wenn das Netzmittel in der für die biologische Wirkung erforderlichen Konzentration eingesetzt wird.    Surprisingly, it was found that when alkyl ethers of copolymers of C 2 -C 4 -alkylene oxides are used as wetting agents in SU-containing solid formulations, there is a pronounced stabilization of the active compound in comparison to other wetting agents.
    This effect is particularly surprising because structurally related compounds such as fatty alcohol ethoxylates (see Comparative Examples 1 and 2) and ethylene oxide / propylene oxide block copolymers do not show this behavior but, in contrast, even lead to a breakdown of the active ingredient. The advantageous effect can be observed especially when, in addition to herbicidal active ingredients, water-soluble inorganic salts such as ammonium sulfate are present. The stabilization becomes particularly clear when the wetting agent is used in the concentration required for the biological effect.

    Durch Mischung der SU mit anderen Wirkstoffen, Alkylethern von Copolymeren von C2-C4-Alkylenoxiden und Ammoniumsulfat lassen sich lagerstabile Fertigformulierungen mit guter biologischer Wirkung erhalten.By mixing the SU with other active ingredients, alkyl ethers of copolymers of C 2 -C 4 alkylene oxides and ammonium sulfate, ready-to-use formulations with good biological effects can be obtained.

    Weiterhin wurden Verfahren zur Herstellung der erfindungsgemäßen festen Mischungen gefunden sowie deren Verwendung als Pflanzenschutzmittel zur Bekämpfung unerwünschter Schadpflanzen.Furthermore, processes for the preparation of the invention found solid mixtures and their use as crop protection agents to combat unwanted harmful plants.

    Als Sulfonylharnstoff a) kommen generell Verbindungen mit der Struktureinheit

    Figure 00030001
    in Betracht.Compounds with the structural unit generally come as sulfonylurea a)
    Figure 00030001
    into consideration.

    Bevorzugt werden SU der folgenden Strukturen I:

    Figure 00030002
    wobei J folgende Bedeutung hat:
    Figure 00040001
    Figure 00040002
    Figure 00040003
    Figure 00040004
    Figure 00040005
    wobei die Substituenten R bis R18 folgende Bedeutung haben:

    R:
    H oder CH3;
    R1:
    F, Cl, Br, NO2, C1-C4-Alkyl, C1-C4-Haloalkyl, C3-C4-Cycloalkyl, C2-C4-Haloalkenyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C2-C4-Alkoxyalkoxy, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18, CH2CN oder L;
    R2:
    H, F, Cl, Br, CN, CH3, OCH3, SCH3, CF3 oder OCF2H;
    R3:
    Cl, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, SO2CH3, SO2CH2CH3, OCH3, or OCH2CH3;
    R4:
    C1-C3-Alkyl, C1-C4-Haloalkyl, C1-C4-Alkoxy, C2-C4-Haloalkenyl, F, Cl, Br, NO2, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 or L;
    R5:
    H, F, Cl, Br oder CH3;
    R6:
    C1-C4-Alkyl, C1-C4-Alkoxy, C2-C4-Haloalkenyl, F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 or L;
    R7:
    H, F, Cl, CH3 oder CF3;
    R8:
    H, C1-C4-Alkyl oder Pyridyl;
    R9:
    ist C1-C4-Alkyl, C1-C4-Alkoxy, F, Cl, Br, NO2, CO2R12, SO2NR15R16, S(O)nR17, OCF2H, C(O)R18, C2-C4-Haloalkenyl oder L;
    R10:
    H, Cl, F, Br, C1-C4-Alkyl or C1-C4-Alkoxy;
    R11:
    H, C1-C4-Alkyl, C1-C4-Alkoxy, C2-C4-Alkoxy; Haloalkenyl, F, Cl, Br, CO2R12 C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 oder L;
    R12:
    C1-C4-Alkyl, ggf. substituiert durch Halogen, C1-C4-Alkoxy or CN, Allyl oder Propargyl;
    R13:
    H, C1-C4-Alkyl oder C1-C4-Alkoxy;
    R14:
    C1-C4-Alkyl;
    R15:
    H, C1-C4-Alkyl, C1-C4-Alkoxy, Allyl oder Cyclopropyl;
    R16:
    H oder C1-C4-Alkyl;
    R17:
    C1-C4-Alkyl, C1-C4-Haloalkyl, Allyl oder Propargyl;
    R18:
    C1-C4-Alkyl, C1-C4-Haloalkyl or C3-C5-Cycloalkyl, ggf. substituiert durch Halogen;
    n
    0,1 oder 2 ist;
    L
    die Struktur II
    Figure 00060001
    hat, wobei
    Rj :
    H oder C1-C3 Alkyl;
    W:
    O oder S;
    X:
    H, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, C1-C4-Haloalkylthio, C1-C4-Alkylthio, Halogen, C2-C5-Alkoxyalkyl, C2-C5-Alkoxyalkoxy, Amino, C1-C3-Alkylamino or Di(C1-C3 alkyl)-Amino;
    Y:
    H, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Alkylthio, C1-C4-Haloalkylthio, C2-C5-Alkoxyalkyl, C2-C5-Alkoxyalkoxy, Amino, C1-C3-Alkylamino, Di(C1-C3-Alkyl)-Amino, C3-C4-Alkenyloxy, C3-C4-Alkanyloxy, C2-C5-Alkylthioalkyl, C2-C5-Alkylsulfinylalkyl, C2-C5-Alkylsulfonylalkyl, C1-C4-Haloalkyl, C2-C4-Alkenyl, C3-C5-Cycloalkyl, Azido, Fluor oder Cyano;
    Z:
    CH oder N; ist,
    und deren landwirtschaftlich brauchbare Salze.SU of the following structures I are preferred:
    Figure 00030002
    where J has the following meaning:
    Figure 00040001
    Figure 00040002
    Figure 00040003
    Figure 00040004
    Figure 00040005
    where the substituents R to R 18 have the following meaning:
    R:
    H or CH 3 ;
    R 1 :
    F, Cl, Br, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 4 cycloalkyl, C 2 -C 4 haloalkenyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 4 alkoxyalkoxy, CO 2 R 12 , C (O) NR 13 R 14 , SO 2 NR 15 R 16 , S (O) n R 17 , C (O) R 18 , CH 2 CN or L;
    R 2 :
    H, F, Cl, Br, CN, CH 3 , OCH 3 , SCH 3 , CF 3 or OCF 2 H;
    R 3 :
    Cl, NO 2 , CO 2 CH 3 , CO 2 CH 2 CH 3 , SO 2 N (CH 3 ) 2 , SO 2 CH 3 , SO 2 CH 2 CH 3 , OCH 3 , or OCH 2 CH 3 ;
    R 4 :
    C 1 -C 3 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 2 -C 4 haloalkenyl, F, Cl, Br, NO 2 , CO 2 R 12 , C (O) NR 13 R 14 , SO 2 NR 15 R 16 , S (O) n R 17 , C (O) R 18 or L;
    R 5 :
    H, F, Cl, Br or CH 3 ;
    R 6 :
    C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 haloalkenyl, F, Cl, Br, CO 2 R 12 , C (O) NR 13 R 14 , SO 2 NR 15 R 16 , S (O) n R 17 , C (O) R 18 or L;
    R 7 :
    H, F, Cl, CH 3 or CF 3 ;
    R 8 :
    H, C 1 -C 4 alkyl or pyridyl;
    R 9 :
    is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, F, Cl, Br, NO 2 , CO 2 R 12 , SO 2 NR 15 R 16 , S (O) n R 17 , OCF 2 H, C (O) R 18 , C 2 -C 4 haloalkenyl or L;
    R 10 :
    H, Cl, F, Br, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
    R 11 :
    H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxy; Haloalkenyl, F, Cl, Br, CO 2 R 12 C (O) NR 13 R 14 , SO 2 NR 15 R 16 , S (O) n R 17 , C (O) R 18 or L;
    R 12 :
    C 1 -C 4 alkyl, optionally substituted by halogen, C 1 -C 4 alkoxy or CN, allyl or propargyl;
    R 13 :
    H, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
    R 14 :
    C 1 -C 4 alkyl;
    R 15 :
    H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, allyl or cyclopropyl;
    R 16 :
    H or C 1 -C 4 alkyl;
    R 17 :
    C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, allyl or propargyl;
    R 18 :
    C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 3 -C 5 cycloalkyl, optionally substituted by halogen;
    n
    Is 0.1 or 2;
    L
    the structure II
    Figure 00060001
    has, where
    R j :
    H or C 1 -C 3 alkyl;
    W:
    O or S;
    X:
    H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylthio, Halogen, C 2 -C 5 alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, C 1 -C 3 alkylamino or di (C 1 -C 3 alkyl) amino;
    Y:
    H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 2 -C 5 alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, C 1 -C 3 alkylamino, di (C 1 -C 3 alkyl) amino, C 3 -C 4 alkenyloxy, C 3 -C 4 alkanyloxy, C 2 - C 5 alkylthioalkyl, C 2 -C 5 alkylsulfinylalkyl, C 2 -C 5 alkylsulfonylalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 5 cycloalkyl, azido, fluorine or cyano ;
    Z:
    CH or N; is
    and their agriculturally useful salts.

    Nachstehend seien einige geeignete SU mit ihrem INN (International Nonproprietary Name) gemäß Pesticide Manual erwähnt :
    ACC 322140;
    Amidosulfuron;
    Azimsulfuron (N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]-carbonyl]-1-methyl-4- (2-methyl-2H-tetrazol-5-yl)-1H-pyrazol-5-sulfonamid);
    Bensulfuron-methyl (Methyl 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]-carbonyl] amino] sulfonyl] methyl] benzoat);
    Ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]benzoat (Chlorimuron ethyl) ;
    2-Chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzolsulfonamid(Chlorsulfuron) ;
    Chlorsulfoxim;
    Cinosulfuron;
    Cyclosulfamuron;
    Ethametsulfuron-methyl (Methyl 2-[[[[[4-ethoxy-6-(methylamino) -1,3,5-triazin-2-yl]amino]carbonyl]amino] sulfonyl]-benzoat);
    Ethoxysulfuron;
    Flazasulfuron;
    Flupyrsulfuron (Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino] -carbonyl] amino] sulfonyl] -6-(trifluormethyl)-3-pyridincarboxylat);
    Halosulfuron-methyl ;
    Imazosulfuron;
    Methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl] amino] sulfonyl]benzoat(Metsulfuron methyl) ;
    Nicosulfuron (2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]-carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridincarboxamid); Oxasulfuron;
    Primisulfuron (Methyl 2-[[[[[4,6-bis(difluormethoxy)-2-pyrimidinyl] amino]carbonyl] amino] sulfonyl] benzoat) ;
    Prosulfuron;
    Pyrazosulfuron-ethyl (Ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]-carbonyl]amino]sulfonyl]-1-methyl-lH-pyrazol-4-carboxylat) ;
    Rimsulfuron (N-[[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinsulfonamid); Sulfosulfuron;
    Sulfometuron-methyl (Methyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)-amino]-carbonyl]amino]sulfonyl]benzoat ();
    Thifensulfuron-methyl (Methyl-3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] carbonyl] amino]sulfonyl]-2-thiophencarboxylat);
    2-(2-Chlorethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]carbonyl]benzolsulfonamid (Triasulfuron);
    Tribenuron-methyl (Methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl] amino] sulfonyl]benzoat) ;
    und
    Triflusulfuron-methyl (Methyl 2-[[[[[4-(dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]-carbonyl]-amino]sulfonyl]-3-methylbenzoat);    Some suitable SUs with their INN (International Nonproprietary Name) according to the Pesticide Manual are mentioned below:
    ACC 322140;
    amidosulfuron;
    Azimsulfuron (N - [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] -1-methyl-4- (2-methyl-2H-tetrazol-5-yl) -1H-pyrazole-5-sulfonamide );
    Bensulfuron-methyl (methyl 2 - [[[[((4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] benzoate);
    Ethyl 2 - [[[[(4-chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate (chlorimuron ethyl);
    2-chloro-N - [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzenesulfonamide (chlorosulfuron);
    Chlorsulfoxim;
    cinosulfuron;
    cyclosulfamuron;
    Ethametsulfuron-methyl (methyl 2 - [[[[[4-ethoxy-6- (methylamino) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] benzoate);
    ethoxysulfuron;
    flazasulfuron;
    Flupyrsulfuron (methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinecarboxylate);
    Halosulfuron-methyl;
    imazosulfuron;
    Methyl 2 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] benzoate (metsulfuron methyl);
    Nicosulfuron (2 - [[[((4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -N, N-dimethyl-3-pyridinecarboxamide); oxasulfuron;
    Primisulfuron (Methyl 2 - [[[[[4,6-bis (difluoromethoxy) -2-pyrimidinyl] amino] carbonyl] amino] sulfonyl] benzoate);
    prosulfuron;
    Pyrazosulfuron-ethyl (ethyl 5 - [[[((4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-1H-pyrazole-4-carboxylate);
    Rimsulfuron (N - [[(4,6-dimethoxy-2-pyrimidinylamino] carbonyl] -3- (ethylsulfonyl) -2-pyridinesulfonamide); sulfosulfuron;
    Sulfometuron-methyl (methyl 2 - [[[[(4,6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate ();
    Thifensulfuron-methyl (methyl-3 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] -2-thiophene carboxylate);
    2- (2-chloroethoxy) -N - [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzenesulfonamide (triasulfuron);
    Tribenuron-methyl (Methyl 2 - [[[[N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N-methylamino] carbonyl] amino] sulfonyl] benzoate);
    and
    Triflusulfuron-methyl (methyl 2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3-methylbenzoate);

    Besonders bevorzugt sind Sulfonylharnstoffe der allgemeinen Formel III (entspricht der Formel I mit J=J1), wie sie z.B aus der EP-A 388 873, der EP-A 559 814, der EP-A 291 851 und der EP-A 446 743 bekannt sind :

    Figure 00080001
    wobei die Substituenten folgende Bedeutung haben:

    R1
    C1-C4-Alkyl, das eine bis fünf der folgenden Gruppen tragen kann: Methoxy, Ethoxy, SO2CH3, Cyano, Chlor, Fluor, SCH3, S(O)CH3;
    Halogen;
    eine Gruppe ER19, in der E O, S oder NR20 bedeutet;
    COOR12 ;
    NO2;
    S(O)nR17, SO2NR15R16, CONR13R14;
    R2
    Wasserstoff, Methyl, Halogen, Methoxy, Nitro, Cyano, Trifluormethyl, Trifluormethoxy, Difluormethoxy oder Methylthio,
    Y
    F, CF3, CF2Cl,CF2H, OCF3; OCF2Cl, C1-C4-Alkyl oder C1-C4-Alkoxy;
    X
    C1-C2-Alkoxy, C1-C2-Alkyl, C1-C2-Alkylthio, C1-C2-Alkylamino, Di-C1-C2-Alkylamino, Halogen, C1-C2-Halogenalkyl, C1-C2-Halogenalkoxy,
    R
    Wasserstoff oder Methyl;
    R19
    C1-C4-Alkyl, C2-C4-Alkenyl, C2-C4-Alkinyl oder C3-C6-Cycloalkyl, welche 1 bis 5 Halogenatome tragen können. Ferner bedeutet R19 im Falle, daß E für O oder NR20 steht, noch Methylsulfonyl, Ethylsulfonyl, Trifluormethylsulfonyl, Allylsulfonyl, Propargylsulfonyl oder Dimethylsulfamoyl;
    R20
    Wasserstoff, Methyl oder Ethyl
    R12
    eine C1-C4-Alkylgruppe, welche bis zu drei der folgenden Reste tragen kann: Halogen, C1-C4-Alkoxy, Allyl oder Propargyl;
    R17
    eine C1-C4-Alkylgruppe, welche einen bis drei der folgenden Reste tragen kann: Halogen, C1-C4-Alkoxy, Allyl oder Propargyl;
    R15
    Wasserstoff, eine C1-C2-Alkoxygruppe oder eine C1-C4-Alkylgruppe;
    R16
    Wasserstoff oder eine C1-C4-Alkylgruppe,
    n
    1 oder 2
    Z
    N, CH
    Sulfonylureas of the general formula III (corresponding to formula I with J = J 1 ), as described, for example, in EP-A 388 873, EP-A 559 814, EP-A 291 851 and EP-A 446, are particularly preferred 743 are known:
    Figure 00080001
    where the substituents have the following meaning:
    R 1
    C 1 -C 4 alkyl, which can carry one to five of the following groups: methoxy, ethoxy, SO 2 CH 3 , cyano, chlorine, fluorine, SCH 3 , S (O) CH 3 ;
    Halogen;
    a group ER 19 in which EO, S or NR 20 ;
    COOR 12 ;
    NO 2 ;
    S (O) n R 17 , SO 2 NR 15 R 16 , CONR 13 R 14 ;
    R 2
    Hydrogen, methyl, halogen, methoxy, nitro, cyano, trifluoromethyl, trifluoromethoxy, difluoromethoxy or methylthio,
    Y
    F, CF 3 , CF 2 Cl, CF 2 H, OCF 3 ; OCF 2 Cl, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
    X
    C 1 -C 2 alkoxy, C 1 -C 2 alkyl, C 1 -C 2 alkylthio, C 1 -C 2 alkylamino, di-C 1 -C 2 alkylamino, halogen, C 1 -C 2 - Haloalkyl, C 1 -C 2 haloalkoxy,
    R
    Hydrogen or methyl;
    R 19
    C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or C 3 -C 6 cycloalkyl, which can carry 1 to 5 halogen atoms. Furthermore, in the case where E is O or NR 20 , R 19 also denotes methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonyl or dimethylsulfamoyl;
    R 20
    Hydrogen, methyl or ethyl
    R 12
    a C 1 -C 4 alkyl group which can carry up to three of the following radicals: halogen, C 1 -C 4 alkoxy, allyl or propargyl;
    R 17
    a C 1 -C 4 alkyl group which can carry one to three of the following radicals: halogen, C 1 -C 4 alkoxy, allyl or propargyl;
    R 15
    Hydrogen, a C 1 -C 2 alkoxy group or a C 1 -C 4 alkyl group;
    R 16
    Hydrogen or a C 1 -C 4 alkyl group,
    n
    1 or 2
    Z
    N, CH

    Insbesondere bevorzugte Sulfonylharnstoffe der Formel III sind solche der allgemeinen Formel I, in denen J für J1 steht und die restlichen Substituenten die folgende Bedeutung haben :

    R1
    CO2CH3,CO2C2H5, CO2iC3H7, CF3, CF2H; OSO2CH3, OSO2N(CH3)2, Cl, NO2, SO2N(CH3)2, SO2CH3 und N(CH3)SO2CH3,
    R2
    Wasserstoff, Cl, F oder C1-C2-Alkyl,
    Y
    CF2H, OCF3, OCF2Cl, CF2Cl, CF3 oder F,
    X
    OCH3, OC2H5, OCF3, OCF2Cl; CF3, Cl, F, NH(CH3), N(CH3)2 oder C1-C2-Alkyl,
    R5
    Wasserstoff, und
    Z
    N oder CH.
    Particularly preferred sulfonylureas of the formula III are those of the general formula I in which J represents J 1 and the remaining substituents have the following meaning:
    R 1
    CO 2 CH 3 , CO 2 C 2 H 5 , CO 2 iC 3 H 7 , CF 3 , CF 2 H; OSO 2 CH 3 , OSO 2 N (CH 3 ) 2 , Cl, NO 2 , SO 2 N (CH 3 ) 2 , SO 2 CH 3 and N (CH 3 ) SO 2 CH 3 ,
    R 2
    Hydrogen, Cl, F or C 1 -C 2 alkyl,
    Y
    CF 2 H, OCF 3 , OCF 2 Cl, CF 2 Cl, CF 3 or F,
    X
    OCH 3 , OC 2 H 5 , OCF 3 , OCF 2 Cl; CF 3 , Cl, F, NH (CH 3 ), N (CH 3 ) 2 or C 1 -C 2 alkyl,
    R 5
    Hydrogen, and
    Z
    N or CH.

    Ganz besonders bevorzugte Verbindungen der Formel III sind in der folgenden Tabelle zusammengestellt.

    Figure 00090001
    Figure 00100001
    Figure 00110001
    Figure 00120001
    Figure 00130001
    Very particularly preferred compounds of the formula III are listed in the following table.
    Figure 00090001
    Figure 00100001
    Figure 00110001
    Figure 00120001
    Figure 00130001

    Selbstverständlich können als Komponente a) auch Mischungen mehrerer Sulfonylharnstoffe eingesetzt werden.Mixtures of several can of course also be used as component a) Sulfonylureas are used.

    Als Komponente b) enthalten die erfindungsgemäßen Festformulierungen einen oder mehrere Alkylether von Copolymeren von C2-C4-Alkylenoxiden, vorzugsweise von statistischen oder Blockcopolymeren von Etxylenoxid und Propylenoxid. Die Alkylgruppe im Etherrest hat in der Regel 10 bis 25, vorzugsweise 12 bis 20 C-Atome und ist vorzugsweise linear. Das molare Verhältnis von Ethylenoxidzu Propylenoxid-Einheiten unterliegt dabei keiner besonderen Beschränkung und liegt üblicherweise im Bereich von 1:10 bis 10:1, vorzugsweise von 1:5 bis 5:1 und insbesondere von 1:3 bis 3:1. Im Falle von Blockcopolymeren liegt die Blocklänge im allgemeinen im Bereich von 2-100 Einheiten pro Block.As component b), the solid formulations according to the invention contain one or more alkyl ethers of copolymers of C 2 -C 4 -alkylene oxides, preferably of statistical or block copolymers of ethylene oxide and propylene oxide. The alkyl group in the ether radical generally has 10 to 25, preferably 12 to 20, carbon atoms and is preferably linear. The molar ratio of ethylene oxide to propylene oxide units is not particularly limited and is usually in the range from 1:10 to 10: 1, preferably from 1: 5 to 5: 1 and in particular from 1: 3 to 3: 1. In the case of block copolymers, the block length is generally in the range of 2-100 units per block.

    Entsprechende Produkte sind dem Fachmann bekannt und in der Literatur beschrieben. Nur beispielsweise sei hier auf McCutheon's, Emulsifiers and Detergents, Volumes 1 und 2 (1994), North American Edition, McCutheon Division, Glen Rock, USA sowie auf "Surfactants in Europe", 2. Auflage 1989, Terg Data, Darlington, UK, verwiesen.Corresponding products are known to the person skilled in the art and in the literature described. Just for example here on McCutheon's, Emulsifiers and Detergents, Volumes 1 and 2 (1994), North American Edition, McCutheon Division, Glen Rock, USA and on "Surfactants in Europe ", 2nd edition 1989, Terg Data, Darlington, UK, directed.

    Geeignete kommerziell erhältliche Produkte sind beispielsweise Antarox® BO (Fa. Rhone Poulenc), Emulsogen® V2436 (Fa. Hoechst), Dehypon® LS und LT (Fa. Henkel), Synperionic® LF (Fa. ICI Specialty Chemicals) und insbesondere die Produkte der Plurafac® LF Reihe der BASF Aktiengesellschaft.Suitable commercially available products are, for example Antarox® BO (Rhone Poulenc), Emulsogen® V2436 (Hoechst), Dehypon® LS and LT (Henkel), Synperionic® LF (ICI Specialty Chemicals) and in particular the products of Plurafac® LF BASF Aktiengesellschaft series.

    Der Anteil der Komponente a) an den erfindungsgemäßen festen Mischungen liegt im allgemeinen im Bereich von 0,5 bis 75 Gew.%,vorzugsweise von 1 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Formulierung.The proportion of component a) in the solid according to the invention Mixtures generally range from 0.5 to 75 % By weight, preferably from 1 to 25% by weight, based on the total weight the wording.

    Der Anteil der Komponente b) liegt im allgemeinen im Bereich von 1 bis 75, insbesondere 1 bis 50 und besonders bevorzugt 5 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Formulierung.The proportion of component b) is generally in the range from 1 to 75, in particular 1 to 50 and particularly preferably 5 to 25 % By weight, based on the total weight of the formulation.

    Neben den Komponenten a) und b) können die erfindungsgemäßen festen Mischungen noch weitere, mit Sulfonylharnstoffen mischbare bzw. synergistisch wirksame andere Wirkstoffe enthalten. Entsprechende Produkte sind dem Fachmann bekannt und in der Literatur beschrieben. Die folgenden Gruppen von weiteren Wirkstoffen seien beispielhaft unter Verwendung ihrer INN (in englischer Sprache) genannt :

  • c1: 1,3,4-Thiadiazole :
  • buthidazole, cyprazole;
  • c2: Amide :
  • allidochlor (CDAA), Benzoylprop-ethyl, Bromobutide, chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide, naptalame, pronamid (propyzamid), propanil;
  • c3: Aminophosphorsäuren :
  • bilanafos (bialaphos); buminafos, glufosinate-ammonium, glyphosate, sulfosate
  • c4: Aminotriazole :
  • Amitrol;
  • c5: Anilide :
  • anilofos, mefenacet, thiafluamide;
  • c6: Aryloxyalkansäuren
    2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, (2.,4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr;
  • c7: Benzoesäuren :
  • chloramben, dicamba;
  • c8: Benziothiadiazinone :
  • Bentazon;
  • c9: Bleacher :
  • clomazone (dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate, sulcotrione (chlor-mesulone) isoxaflutol, 2-(2'-Chlor-3'-Ethoxy-4'-ethylsulfonyl-benzoyl)-4-methylcyclohexan-1,3-dion;
  • c10: Carbamate :
  • asulam, barban, butylate, carbetamide, chlorbufam, chlorpropham, cycloate, desmedipham, diallate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham, prosulfocarb, pyributicarb, sulfallate (CDEC), terbucarb, thiobencarb (benthiocarb), tiocarbazil, triallate, vernolate;
  • c11: Chinolinsäuren :
  • quinclorac, quinmerac;
  • c12: Chloracetanilide :
  • acetochlor, alachlor, butachlor, butenachlor, diethatyl ethyl, dimethachlor, dimethenamide (vgl. auch unter Kategorie c2) metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor;
  • c13:Cyclohexenone :
  • alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-Chlor-phenoxy) propyloxyimino] butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-on;
  • c14: Dichlorpropionsäuren :
  • dalapon;
  • c15: Dihydrobenzofurane :
  • ethofumesate;
  • c16: Dihydrofuran-1-one :
  • flurtamone;
  • c17: Dinitroaniline :
  • benefin, butralin, dinitramin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin;
  • c18: Dinitrophenole:
  • bromofenoxim, dinoseb, dinoseb-acetat, dinoterb, DNOC;
  • c19: Diphenylether :
  • acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;
  • c20: Dipyridylene :
  • cyperquat, difenzoquat-methylsulfat, diquat, paraquat-dichlorid;
  • c21: Harnstoffe :
  • benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymron, ethidimuron, fenuron, fluormeturon, isoproturon, isouron, karbutilat, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon;
  • c22: Imidazole :
  • iscarbamide;
  • c23: Imidazolinone :
  • imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl (imazame),imazethapyr, imazamox;
  • c24: Oxadiazole :
  • methazole, oxadiargyl, oxadiazone;
  • c25: Oxirane :
  • tridiphane
  • c26: Phenole :
  • bromoxynil, ioxynil;
  • c27: Phenoxypropionsäureester
    clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifopp-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, guizalofop-p-ethyl, quizalofoptefuryl;
  • c28: Phenylessigsäuren :
  • chlorfenac (fenac);
  • c29: Phenylpropionsäuren :
  • chlorophenprop-methyl;
  • c30: Protoporphyrinogen-IX-Oxydase-Hemmer :
  • benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimine, carfentrazone, azafenidin;
  • c31: Pyrazole :
  • nipyraclofen;
  • c32: Pyridazine :
  • chloridazon, maleic hydrazide, norflurazon, pyridate;
  • c33: Pyridincarbonsäuren:
  • clopyralid, dithippyr, picloram, thaizopyr;
  • c34: Pyrimidylether :
  • pyrithiobac-acid, pyrithiobac-sodium, pyriminobac-methyl, bispyribenzoxim, bispyribac-sodium;
  • c35: Sulfonamide :
  • flumetsulam, metosulam, cloransulam-methyl, diclosulam;
  • c36: Triazine :
  • ametryn, atrazin, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn, dipropetryn, eglinazin-ethyl, hexazinon, procyazine, prometon, prometryn, propazin, secbumeton, simazin, simetryn, terbumeton, terbutryn, terbutylazin, trietazin, dimesyflam;
  • c37: Triazinone :
  • ethiozin, metamitron, metribuzin;
  • c38: Triazolcarboxamide :
  • triazofenamid;
  • c39: Uracile:
  • bromacil, lenacil, terbacil;
  • c40: Verschiedene :
  • benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide, perfluidone, piperophos, diflufenzopyr, diflufenzopyr-natrium
    • oder die umweltverträglichen Salze der vorstehend genannten Wirkstoffgruppen.In addition to components a) and b), the solid mixtures according to the invention may also contain other active ingredients which are miscible with synergistic or sulfonylureas. Corresponding products are known to the person skilled in the art and are described in the literature. The following groups of other active ingredients are mentioned by way of example using their INN (in English):
  • c1: 1,3,4-thiadiazoles:
  • buthidazole, cyprazole;
  • c2: Amides:
  • allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorothiamide, dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide, naptalame, pronamid (propyzamid), propanil;
  • c3: aminophosphoric acids:
  • bilanafos (bialaphos); buminafos, glufosinate-ammonium, glyphosate, sulfosate
  • c4: aminotriazoles:
  • amitrole;
  • c5: anilides:
  • anilofos, mefenacet, thiafluamide;
  • c6: aryloxyalkanoic acids
    2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, (2nd, 4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr;
  • c7: benzoic acids:
  • chloramben, dicamba;
  • c8: Benziothiadiazinone:
  • bentazone;
  • c9: bleacher:
  • clomazone (dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate, sulcotrione (chloromesulone) isoxaflutole, 2- (2'-chloro-3'-ethoxy-4'-ethylsulfonyl-benzoyl) -4-methylcyclohexane-1, 3-dione;
  • c10: carbamates:
  • asulam, barban, butylate, carbetamide, chlorobufam, chlorpropham, cycloate, desmedipham, dialallate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham, prosulfocarb, pyributicarb, sulfallate (CDEC), terbucarbhi, carboben tiocarbazil, triallate, vernolate;
  • c11: quinolinic acids:
  • quinclorac, quinmerac;
  • c12: chloroacetanilides:
  • acetochlor, alachlor, butachlor, butenachlor, diethyl ethyl, dimethachlor, dimethenamide (see also under category c2) metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor;
  • c13: cyclohexenones:
  • alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2- {1- [2- (4-chlorophenoxy) propyloxyimino] butyl} -3-hydroxy-5- (2H-tetrahydrothiopyran-3-yl) - 2-cyclohexen-1-one;
  • c14: dichloropropionic acids:
  • dalapon;
  • c15: dihydrobenzofurans:
  • ethofumesate;
  • c16: dihydrofuran-1-one:
  • flurtamone;
  • c17: Dinitroaniline:
  • benefin, butralin, dinitramine, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin;
  • c18: dinitrophenols:
  • bromofenoxime, dinoseb, dinoseb acetate, dinoterb, DNOC;
  • c19: diphenyl ether:
  • acifluorfen-sodium, aclonifen, bifenox, chloronitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;
  • c20: Dipyridylene:
  • cyperquat, difenzoquate methyl sulfate, diquat, paraquat dichloride;
  • c21: ureas:
  • benzthiazuron, buturon, chlorbromuron, chloroxuron, chlorotoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymron, ethidimuron, fenuron, fluorometuron, isoproturon, isouron, carbutilat, linuron, metabenzuronuronuronuronuronuronuronuron tebuthiuron, trimeturon;
  • c22: Imidazole:
  • iscarbamide;
  • c23: imidazolinones:
  • imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl (imazame), imazethapyr, imazamox;
  • c24: oxadiazoles:
  • methazole, oxadiargyl, oxadiazone;
  • c25: oxiranes:
  • tridiphane
  • c26: phenols:
  • bromoxynil, ioxynil;
  • c27: phenoxypropionic acid ester
    clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifopp-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafizop ethyl, guizalofop-p-ethyl, quizalofoptefuryl;
  • c28: phenylacetic acids:
  • chlorfenac (fenac);
  • c29: phenylpropionic acids:
  • chlorophenprop-methyl;
  • c30: Protoporphyrinogen IX oxidase inhibitor:
  • benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimine, carfentrazone, azafenidin;
  • c31: pyrazoles:
  • nipyraclofen;
  • c32: pyridazines:
  • chloridazon, maleic hydrazide, norflurazon, pyridate;
  • c33: pyridinecarboxylic acids:
  • clopyralid, dithippyr, picloram, thaizopyr;
  • c34: pyrimidyl ether:
  • pyrithiobac-acid, pyrithiobac-sodium, pyriminobac-methyl, bispyribenzoxim, bispyribac-sodium;
  • c35: sulfonamides:
  • flumetsulam, metosulam, cloransulam-methyl, diclosulam;
  • c36: triazines:
  • ametryn, atrazin, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn, dipropetryn, eglinazin-ethyl, hexazinon, procyazine, prometon, prometryn, propazin, secbumeton, simazin, simetryn, terbumeton, terbutryn, terbutylazin, trietamine, trietamine;
  • c37: triazinones:
  • ethiozin, metamitron, metribuzin;
  • c38: triazole carboxamides:
  • triazofenamid;
  • c39: Uracile:
  • bromacil, lenacil, terbacil;
  • c40: various:
  • benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorothal-dimethyl (DCPA), cinmethylin, dichlobenil, endothall, fluorobentranil, mefluidide, perfluidone, piperophos, diflufenzopyr, diflufenzopyr-sodium
    • or the environmentally compatible salts of the above-mentioned groups of active ingredients.

    Bevorzugte weitere Wirkstoffe c) sind z.B.
    bromobutide, dimethenamide, isoxaben, propanil, glufosinate-ammonium, glyphosate, sulfosate, mefenacet,thiafluamide,
    2,4-D, 2,4-DB, dichlorprop, dichlorprop-P,
    dichlorprop-P(2,4-DP-P), fluoroxopyr, MCPA, mecoprop, mecoprop-P, dicamba,
    Bentazon,
    clomazone, diflufenican, sulcotrione, isoxaflutole, phenmedipham, thiobencarb,
    quinclorac, quinmerac,
    acetochlor, alachlor, butachlor, metazachlor, metolachlor, pretilachlor,
    butroxydim, caloxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-Chlor-phenoxy) propyloxyimino] butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-on, pendimethalin,
    acifluorfen-sodium, bifenox, fluoroglycofen-ethyl, fomesafen, lactofen,
    chlortoluron, cycluron, dymron, isoproturon, metabenzthiazuron, imazaquin, imazamox, imazethabenz-methyl, imazethapyr, bromoxynil, ioxynil,
    clodinafop, cyhlaofop-butyl, fenoxyprop-ethyl, fenoxaprop-p-ethyl, haloxyfop-p-methyl,
    cinidon-ethyl, flumiclorac-pentyl, carfentrazone, flumipropyn, fluthiacet-methyl,
    pyridate,
    clopyralid,
    bispyribac-sodium, pyriminobac-methyl,
    flumetsulam, metosulam,
    atrazin, cyanazine, terbutylazine,
    benazolin, benfuresate, cafenstrole, cinemthylin, ammonium-bentazon, cloquintocet, diflufenzopyr, diflufenzopyr-Natrium, pyraflufen-ethyl.    Preferred further active ingredients c) are, for example
    bromobutide, dimethenamide, isoxaben, propanil, glufosinate-ammonium, glyphosate, sulfosate, mefenacet, thiafluamide,
    2,4-D, 2,4-DB, dichlorprop, dichlorprop-P,
    dichlorprop-P (2,4-DP-P), fluoroxopyr, MCPA, mecoprop, mecoprop-P, dicamba,
    bentazone,
    clomazone, diflufenican, sulcotrione, isoxaflutole, phenmedipham, thiobencarb,
    quinclorac, quinmerac,
    acetochlor, alachlor, butachlor, metazachlor, metolachlor, pretilachlor,
    butroxydim, caloxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, 2- {1- [2- (4-chlorophenoxy) propyloxyimino] butyl} -3-hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2- cyclohexen-1-one, pendimethalin,
    acifluorfen-sodium, bifenox, fluoroglycofen-ethyl, fomesafen, lactofen,
    chlorotoluron, cycluron, dymron, isoproturon, metabenzthiazuron, imazaquin, imazamox, imazethabenz-methyl, imazethapyr, bromoxynil, ioxynil,
    clodinafop, cyhlaofop-butyl, fenoxyprop-ethyl, fenoxaprop-p-ethyl, haloxyfop-p-methyl,
    cinidon-ethyl, flumiclorac-pentyl, carfentrazone, flumipropyn, fluthiacet-methyl,
    pyridate,
    clopyralid,
    bispyribac-sodium, pyriminobac-methyl,
    flumetsulam, metosulam,
    atrazine, cyanazine, terbutylazine,
    benazolin, benfuresate, cafenstrole, cinemthylin, ammonium-bentazon, cloquintocet, diflufenzopyr, diflufenzopyr-sodium, pyraflufen-ethyl.

    Insbesondere bevorzugt sind folgende Verbindungen c) :

  • 2,4-D, Dichlorprop-P, MCPA, mecoprop-P,
  • dicamba,
  • bentazon,
  • diflufenican, sulcotrione,
  • quinclorac,
  • caloxydim, cycloxydim, sethoxydim, 2-{1-[2-(-(4-Chlor-phenoxy) propyloxyimino] butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-on;
  • acifluorfen-sodium, fluoroglycofen-ethyl,
  • bromoxynil,
  • fenoxyprop-ethyl,
  • cinidon-ethyl,
  • Atrazin, terbutylazin,
  • ammonium-bentazon, cloquintocet,
  • thiafluamid, isoxaflutole, diflufenzopyr, diflufenzopyr-Na, carfentrazone, imazamox.
    • The following compounds c) are particularly preferred:
  • 2,4-D, dichloroprop-P, MCPA, mecoprop-P,
  • dicamba,
  • bentazone,
  • diflufenican, sulcotrione,
  • quinclorac,
  • caloxydim, cycloxydim, sethoxydim, 2- {1- [2 - (- (4-chlorophenoxy) propyloxyimino] butyl} -3-hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2-cyclohexen-1- one;
  • acifluorfen-sodium, fluoroglycofen-ethyl,
  • bromoxynil,
  • fenoxyprop-ethyl,
  • cinidon-ethyl,
  • Atrazine, terbutylazin,
  • ammonium bentazone, cloquintocet,
  • thiafluamide, isoxaflutole, diflufenzopyr, diflufenzopyr-Na, carfentrazone, imazamox.

    • Ganz besonders bevorzugt sind folgende Verbindungen c):

  • 2,4-D, dichlorprop-P, Mecoprop-P, MCPA, ammonium-bentazon, Bentazon, diflufenican, quinclorac, 2-{1-[2-(-(4-Chlor-phenoxy) propyloxyimino] butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-on, caloxydim, cycloxydim, sethoxydim, fluoroglycofen-ethyl, cinidon-ethyl, atrazin und terbutylazine, dicamba, diflufenzopyr, diflufenzopyr-Na.
    • The following compounds c) are very particularly preferred:
  • 2,4-D, dichloroprop-P, mecoprop-P, MCPA, ammonium bentazone, bentazone, diflufenican, quinclorac, 2- {1- [2 - (- (4-chlorophenoxy) propyloxyimino] butyl} -3- hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2-cyclohexen-1-one, caloxydim, cycloxydim, sethoxydim, fluoroglycofen-ethyl, cinidon-ethyl, atrazine and terbutylazine, dicamba, diflufenzopyr, diflufenzopyr-Na.

    • Der Anteil der weiteren Wirkstoffe c), wenn solche vorhanden sind, liegt im allgemeinen im Bereich von 0,5 bis 75, vorzugsweise von 1 bis 60 Gew.% der Formulierung. The proportion of other active ingredients c), if any are generally in the range of 0.5 to 75, preferably from 1 to 60% by weight of the formulation.

    Neben den vorstehend beschriebenen Komponenten a), b) und c) können die erfindungsgemäßen festen Mischungen noch an sich bekannte Formulierungshilfsmittel enthalten.In addition to the components a), b) and c) described above the solid mixtures according to the invention still known per se Formulation aids included.

    Als oberflächenaktive Stoffe kommen dabei die Alkali-, Erdalkalioder Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin--, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren von Arylsulfonaten, von Alkylethern, von Laurylethern, von Fettalkoholsulfaten und von Fettalkoholglykolethersulfaten, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphtalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Kondensationsprodukte des Phenols oder der Phenolsulfonsäure mit Formaldehyd, Kondensationsprodukte des Phenols mit Formaldehyd und Natriumsulfit, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Tributylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, ethoxyliertes Rizinusöl, ethoxylierte Triarylphenole, Salze phosphatierter Triarylphenolethoxylate, Laurylalkoholpolyglykoletheracetat, Sorbitester, Ligninsulfit-Ablaugen oder Methylcellulose oder deren Mischungen in Betracht.Alkali, alkaline earth or come as surface-active substances Ammonium salts of aromatic sulfonic acids, e.g. Lignin--, Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as from Fatty acids of aryl sulfonates, of alkyl ethers, of lauryl ethers, of fatty alcohol sulfates and of fatty alcohol glycol ether sulfates, Condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, Condensation products of phenol or phenolsulfonic acid with Formaldehyde, condensation products of phenol with formaldehyde and sodium sulfite, polyoxyethylene octylphenol ether, ethoxylated Isooctyl, octyl or nonylphenol, tributylphenyl polyglycol ether, Alkylaryl polyether alcohols, isotridecyl alcohol, ethoxylated Castor oil, ethoxylated triarylphenols, phosphated salts Triarylphenol ethoxylates, lauryl alcohol polyglycol ether acetate, sorbitol esters, Lignin sulfite leaching or methyl cellulose or their Mixtures into consideration.

    Bei Mitverwendung oberflächenaktiver Stoffe liegt deren Anteil im allgemeinen im Bereich von 0,5 bis 25 Gew.%, bezogen auf das Gesamtgewicht der festen Mischung.If surface-active substances are used, their share is in generally in the range from 0.5 to 25% by weight, based on the total weight the solid mixture.

    Die erfindungsgemäßen festen Mischungen können auch zusammen mit Trägermaterialien verwendet werden. Beispielhaft seien als Trägerstoffe erwähnt:

  • Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kreide, Löß, Ton, Dolomit, Diatomeenerde, Calciumsulfat, Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Thioharnstoff und Harnstoff, pflanzliche Produkte wie Getreidemehle, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver, Attapulgite, Montmorillonite, Glimmer, Vermiculite, synthetische Kieselsäuren und synthetische Calciumsilicate oder deren Mischungen.
    • The solid mixtures according to the invention can also be used together with carrier materials. The following may be mentioned as examples of carriers:
  • Mineral soils such as silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, chalk, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, thiourea and products like urea Cereal flours, tree bark, wood and nutshell flours, cellulose powder, attapulgite, montmorillonite, mica, vermiculite, synthetic silicas and synthetic calcium silicates or mixtures thereof.

    • Als weitere Zusatzstoffe in an sich üblichen Mengen können ferner eingesetzt werden :As further additives in amounts customary per se can also can be used:

    Wasserlösliche Verbindungen oder Salze wie :

  • Natriumsulfat, Kaliumsulfat, Natriumchlorid, Kaliumchlorid, Natriumacetat, Ammoniumhydrogensulfat, Ammoniumchlorid, Ammoniumacetat, Ammoniumformiat, Ammoniumoxalat, Ammoniumcarbonat, Ammoniumhydrogencarbonat, Ammoniumthiosulfat, Ammoniumhydrogendiphosphat, Ammoniumdihydrogenmonophosphat, Ammoniumnatriumhydrogenphosphat, Ammoniumthiocyanat, Ammoniumsulfamat oder Ammoniumcarbamat;
    • Water soluble compounds or salts like:
  • Sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium acetate, ammonium hydrogen sulfate, ammonium chloride, ammonium acetate, ammonium formate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, ammonium thiosulfate, ammonium hydrogen diphosphate, ammonium dihydrogen monophosphate, ammonium sodium ammonium ammonium phosphate, ammonium ammonium phosphate, ammonium ammonium phosphate,

    • Bindemittel, wie :Binders such as:

    Polyvinylpyrrolidon, Polyvinylalkohol, partiell hydrolysiertes PolyvinylacetatCarboxymethylcellulose, Stärke, Vinylpyrrolidon/Vinylacetat-Copolymere und Polyvinylacetat oder deren Mischungen;Polyvinyl pyrrolidone, polyvinyl alcohol, partially hydrolyzed Polyvinyl acetate carboxymethyl cellulose, starch, vinyl pyrrolidone / vinyl acetate copolymers and polyvinyl acetate or mixtures thereof;

    Schmiermittel, wie :Lubricants such as:

    Mg-Stearat, Na-Stearat, Talkum oder Polyethylenglykol oder deren Mischungen;Mg stearate, Na stearate, talc or polyethylene glycol or their mixtures thereof;

    Entschäumer, wie :Defoamers, such as:

    Silikonemulsionen, langkettige Alkohole, Phosphorsäureester, Acetylendiole, Fettsäuren oder fluororganische Verbindungen,
    und    Silicone emulsions, long-chain alcohols, phosphoric acid esters, acetylenediols, fatty acids or organofluorine compounds,
    and

    Komplexbildner, wie :Complexing agents such as:

    Salze der Ethylendiamintetraessigsäure (EDTA), Salze der Trinitrilotriessigsäure oder Salze von Polyphosphorsäuren oder deren Mischungen.Salts of ethylenediaminetetraacetic acid (EDTA), salts of trinitrilotriacetic acid or salts of polyphosphoric acids or their Mixtures.

    Die erfindungsgemäßen festen Mischungen können in Form von Pulver, Granulat, Briketts, Tabletten und ähnliche Formulierungsvarianten hergestellt werden. Neben Pulvern sind dabei Granulate besonders bevorzugt. Bei den Pulvern kann es sich um wasserlösliche oder wasserdispergierbare Pulver handeln. Bei den Granulaten kann es sich um wasserlösliche oder wasserdispergierbare Granulate zum Einsatz in der Spritzapplikation oder um sog. Streugranulate zur Direktapplikation handeln. Die mittlere Teilchengröße der Granulate liegt im allgemeinen zwischen 200 µm und 2 mm.The solid mixtures according to the invention can be in the form of powder, Granules, briquettes, tablets and similar formulation variants getting produced. In addition to powders, there are granules particularly preferred. The powders can be water-soluble or water-dispersible powders. With the granules can be water-soluble or water-dispersible granules for use in spray application or around so-called scatter granules act for direct application. The average particle size the granules are generally between 200 microns and 2 mm.

    Die erhaltenen Granulatformulierungen sind staubfreie, freifließende, nicht verbackende Produkte, die in kaltem Wasser gut löslich bzw. dispergierbar sind.The granule formulations obtained are dust-free, free-flowing, non-caking products that are readily soluble in cold water or are dispersible.

    Aufgrund ihrer Eigenschaften können die Produkte leicht in größeren Mengen abgefüllt werden. Neben Gebinden wie Kunststoff-, Papier-, Laminatsäcken oder Beuteln können sie in Kartons oder anderen Bulk-Containern gehandhabt werden. Um eine Exposition des Anwenders weiter zu vermeiden, ist es möglich, die Produkte in wasserlöslichen Folienbeuteln, wie z.B. Polyvinylalkohol-Folienbeuteln, zu verpacken, die direkt in den Spritztank gegeben werden und sich dort auflösen. Für solche wasserlöslichen Folien können eingesetzt werden u.a. Polyvinylalkohol oder Cellulose-Derivaten wie Methylcellulose, Methyl-hydroxypropyl-cellulose oder Carboxymethylcellulose. Durch Portionierung in anwendungsgerechter Größe kommt der Anwender nicht mehr mit dem Produkt in Berührung. Vorzugsweise werden die wasserlöslichen Beutel in einer wasserdampfundurchlässigen äußeren Hülle wie Polyethylen-Folie, polyethylen-laminiertes Papier oder Alufolie verpackt.Because of their properties, the products can easily be larger Quantities are filled. In addition to containers such as plastic, paper, Laminate bags or pouches can be found in boxes or other Bulk containers are handled. To expose the To further avoid user, it is possible to put the products in water-soluble foil bags, e.g. Polyvinyl alcohol film pouches, to pack, which are put directly into the spray tank and dissolve there. For such water-soluble films can be used i.a. Polyvinyl alcohol or cellulose derivatives such as methyl cellulose, methyl hydroxypropyl cellulose or Carboxymethylcellulose. By portioning in an application-appropriate Size means that the user no longer comes into contact with the product. Preferably, the water soluble bags are in one water vapor impermeable outer shell such as polyethylene film, packed in polyethylene-laminated paper or aluminum foil.

    Die erfindungsgemäßen Festformulierungen lassen sich nach verschiedenen, dem Fachmann bekannten Verfahren herstellen.The solid formulations according to the invention can be produce various methods known to those skilled in the art.

    Als bevorzugte Herstellverfahren für die genannten Formulierungen sind die Extrudergranulation, Sprühtrocknung, Wirbelschichtagglomeration, Mischergranulation und die Tellergranulation zu nennen.As a preferred manufacturing process for the formulations mentioned are extruder granulation, spray drying, fluid bed agglomeration, Mixer granulation and plate granulation.

    Besonders geeignet ist die Wirbelschichtgranulation (WSG). Je nach gewünschter Zusammensetzung der Formulierung wird eine wässrige Lösung, Emulsion oder Suspension, die alle Rezepturbestandteile enthält, in einer WSG-Apparatur versprüht und agglomeriert.Fluidized bed granulation (WSG) is particularly suitable. ever according to the desired composition of the formulation aqueous solution, emulsion or suspension, all of which are components of the formulation contains, sprayed and agglomerated in a WSG apparatus.

    Wahlweise können aber auch Wirkstoffsalze und/oder anorganische Ammoniumsalze in der Apparatur vorgelegt werden und mit einer Lösung oder Emulsion/Suspension der restlichen Rezepturbestandteile besprüht und dabei agglomeriert werden. Ferner ist es möglich, wässrige Lösungen, Emulsionen oder Suspensionen, die bestimmte Rezepturbestandteile enthalten, nacheinander auf ein Wirkstoffgranulat, ein Wirkstoffsalz und/oder ein anorganisches Ammoniumsalz aufzutragen und so verschiedene umhüllende Schichten zu erhalten.Optionally, however, active ingredient salts and / or inorganic Ammonium salts are presented in the apparatus and with a Solution or emulsion / suspension of the remaining ingredients of the formulation sprayed and agglomerated. Furthermore, it is possible aqueous solutions, emulsions or suspensions that contain certain recipe components, one after the other Active ingredient granules, an active ingredient salt and / or an inorganic Apply ammonium salt and so different enveloping layers to obtain.

    Im allgemeinen erfolgt im Zuge der Wirbelschichtgranulierung eine ausreichende Trocknung des Granulats. Es kann jedoch vorteilhaft sein, der Granulation einen separaten Trocknungsschritt im gleichen oder in einem separaten Trockner nachzuschalten. Im Anschluß an die Granulation/Trocknung wird das Produkt abgekühlt und gesiebt.In general, in the course of the fluidized bed granulation sufficient drying of the granules. However, it can be beneficial be a separate drying step in the same granulation or downstream in a separate dryer. In connection after granulation / drying, the product is cooled and sieved.

    Ein weiteres besonders geeignetes Verfahren ist die Extrudergranulation. Zur Extrudergranulierung eignen sich vorzugsweise Korb-, Radial- oder Dome-Extruder mit geringer Verdichtung des Granulatkorns.Another particularly suitable method is extruder granulation. Are preferably suitable for extruder granulation Basket, radial or dome extruder with low compression of the Granule.

    Zur Granulation wird eine Feststoffmischung in einem geeigneten Mischer mit einer Granulierflüssigkeit angeteigt, bis eine extrudierbare Masse entsteht. Diese wird in einem der genannten Extruder extrudiert. Zur Extrusion werden Lochgrößen zwischen 0,3 und 3 mm verwendet (vorzugsweise 0,5-1,5mm) . Als Feststoffmischungen dienen Gemische aus Wirkstoffen, Formulierungshilfsmitteln und ggf. wasserlöslichen Salzen. Diese werden im allgemeinen vorgemahlen. Teilweise ist es ausreichend, wenn nur die wasserunlöslichen Stoffe in geeigneten Mühlen vorgemahlen werden.For the granulation, a solid mixture in a suitable Mixer pasted with a granulating liquid until an extrudable Mass arises. This is in one of the extruders mentioned extruded. Hole sizes between 0.3 are used for extrusion and 3 mm used (preferably 0.5-1.5mm). As solid mixtures serve mixtures of active ingredients, formulation aids and possibly water-soluble salts. These are generally pre-ground. Sometimes it is sufficient if only the water-insoluble ones Materials are pre-ground in suitable mills.

    Als Granulierflüssigkeit eignet sich Wasser, die erfindungsgemäßen Alkylether von Alkylenoxiden oder wässrige Lösungen davon. Weiterhin geeignet sind wässrige Lösungen von anorg. Salzen, nichtionischen Tensiden, anionischen Tensiden, Lösungen von Bindemitteln wie Polyvinylpyrrolidon, Polyvinylalkohol, Carboxymethylcellulose, Stärke, Vinylpyrrolidin/Vinylacetat-Copolymere, Zucker, Dextrin oder Polyethylenglykol. Nach Extrudergranulation wird das erhaltene Granulat getrocknet und ggf. gesiebt um von Grob- und Feinanteil abzutrennen.Water, the ones according to the invention, are suitable as the granulating liquid Alkyl ethers of alkylene oxides or aqueous solutions thereof. Aqueous solutions from anorg are also suitable. Salt, non-ionic surfactants, anionic surfactants, solutions of binders such as polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, Starch, vinyl pyrrolidine / vinyl acetate copolymers, Sugar, dextrin or polyethylene glycol. After extruder granulation the granules obtained are dried and, if necessary, sieved in order to Separate coarse and fine particles.

    Vergleichsbeispiel 1 :Comparative Example 1:

    Eine Vormischung bestehend aus: 73,1 g SU 1 (Verbindung Nr. 47 aus Tabelle 1) (techn. 95,7%) 8 g Tamol® NH 17,9 g Ufoxane® 3A wurde gemischt und in einer Rotorschnellmühle vermahlene.A premix consisting of: 73.1 g SU 1 (compound no. 47 from table 1) (technical 95.7%) 8 g Tamol® NH 17.9 g Ufoxane® 3A was mixed and ground in a high-speed rotor mill.

    Im weiteren wurden: 7,1 g Vormischung1 5 g Extrusil® (Degussa) 77,9 g Ammoniumsulfat in einem Moulinette Haushaltsmischer mit 28g LutensolR ON 80 als 50%ige wässrige Lösung vermischt. Die erhaltene Masse wurde mittels eines Extruders (KAR-75, Fitzpatrick Europe) extrudiert. Die erhaltenen feuchten Granulate wurden im Trockenschrank getrocknet.Furthermore: 7.1 g Vormischung1 5 g Extrusil® (Degussa) 77.9 g ammonium sulfate mixed in a Moulinette household mixer with 28g Lutensol R ON 80 as a 50% aqueous solution. The mass obtained was extruded using an extruder (KAR-75, Fitzpatrick Europe). The moist granules obtained were dried in a drying cabinet.

    Vergleichsbeispiel 2Comparative Example 2

    Eine Vormischung bestehend aus: 73,1 g SU 1 (techn. 95,7%) 8 g Tamol® NH 17,9 g Ufoxane® 3A wurde gemischt und in einer Rotorschnellmühle vermahlen.A premix consisting of: 73.1 g SU 1 (technical 95.7%) 8 g Tamol® NH 17.9 g Ufoxane® 3A was mixed and ground in a high-speed rotor mill.

    Im weiteren wurden: 7,1 g Vormischung 15 g Extrusil® (Degussa) 77,9 g Ammoniumsulfat in einem Moulinette Haushaltsmischer mit 29g Lutensol ON 60 als 50%ige wässrige Lösung vermischt. Die erhaltene Masse wurde mittels eines Extruders (KAR-75, Fitzpatrick Europe) extrudiert. Die erhaltenen feuchten Granulate wurden im Trockenschrank getrocknet.Furthermore: 7.1 g premix 15 g Extrusil® (Degussa) 77.9 g ammonium sulfate mixed in a Moulinette household mixer with 29g Lutensol ON 60 as a 50% aqueous solution. The mass obtained was extruded using an extruder (KAR-75, Fitzpatrick Europe). The moist granules obtained were dried in a drying cabinet.

    Vergleichsbeispiel 3Comparative Example 3

    Eine Vormischung bestehend aus: 73,1 g SU 1 (techn. 95,7%) 8 g Tamol® NH 17,9 g Ufoxane® 3A wurde gemischt und in einer Rotorschnellmühle vermahlen.
    Im weiteren wurden: 7,1 g Vormischung 5 g Tamol® NH 58,9 g Ammoniumsulfat 1 g Antischaumemulsion SRE 3 g Sipernat® 22 25 g Pluronic®PE 6800 in einem Moulinette Haushaltsmischer mit 21 ml Wasser angeteigt. Die erhaltene Masse wurde mittels eines Extruders (KAR 75, Fitzpatrick Europe) extrudiert. Die erhaltenen Granulate wurden in einem Trockenschrank getrocknet.    A premix consisting of: 73.1 g SU 1 (technical 95.7%) 8 g Tamol® NH 17.9 g Ufoxane® 3A was mixed and ground in a high-speed rotor mill.
    Furthermore: 7.1 g premix 5 g Tamol® NH 58.9 g ammonium sulfate 1 g Antifoam emulsion SRE 3 g Sipernat® 22 25 g Pluronic®PE 6800 pasted in a Moulinette household mixer with 21 ml of water. The mass obtained was extruded using an extruder (KAR 75, Fitzpatrick Europe). The granules obtained were dried in a drying cabinet.

    Beispiel 1example 1

    Eine Vormischung bestehend aus: 225 g destilliertem Wasser 13 g SU 1 (techn. 95,7%) 13 g Tamol® NH 26 g Ufoxane® 3A 2,1 g Antischaumemulsion SRE 37,5 g Extrusil® 62,5 g Wettol® LF 700 wurde gemischt und in einer Perlmühle vermahlen. Die entstandene Suspension wurde später als Sprühmischung verwendet.A premix consisting of: 225 g distilled water 13 g SU 1 (technical 95.7%) 13 g Tamol® NH 26 g Ufoxane® 3A 2.1 g Antifoam emulsion SRE 37.5 g Extrusil® 62.5 g Wettol® LF 700 was mixed and ground in a bead mill. The resulting suspension was later used as a spray mixture.

    In einem Laborwirbelschichtgranulator Combi Coata®, Fa. Niro Aeromatic) wurden 100 g pulverförmiges Ammomiumsulfat vorgelegt. Über dem Wirbelboden befand sich eine Zweistoffdüse. Die Vorlage wurde mit Luft von 120°C gewirbelt. Der Sprühdruck der Zweistoffdüse wurde auf 200 kPa eingestellt, die Sprühmischung in die Wirbelschicht eingesprüht und das Wasser verdampft. Das erhaltene Granulat wurde zur Abtrennung des Feinanteils über ein Sieb mit einer Maschenweite von 0,2 mm abgesiebt.In a Combi Coata® laboratory fluidized bed granulator from Niro Aeromatic), 100 g of powdered ammonium sulfate were introduced. There was a two-fluid nozzle above the vortex floor. The template was whirled with air at 120 ° C. The spray pressure of the two-fluid nozzle was set to 200 kPa, the spray mixture in the Fluidized bed sprayed in and the water evaporates. The received Granules were removed using a sieve to remove the fine fraction sieved with a mesh size of 0.2 mm.

    Die nachstehende Tabelle erläutert die in den Beispielen eingesetzten Komponenten : Name chem. Bezeichnung Bezugsquelle Tamol® NH Naphthalinsulfonsäure-Formaldehyd-Kondensat BASF AG Ufoxane® 3A Na-Ligninsulfonat Borregaard Extrusil® hochdisperses Calciumsilicat Degussa Sipernat® 22 hochdisperse Kieselsäure Degussa Antischaummittel SRE Silikonölemulsion Wacker-Chemie Lutensol® ON 60 Fettalkoholethoxylat (6EO) BASF AG Lutensol® ON 80 Fettalkoholethoxylat (8EO) BASF AG Aerosol® OT-B Dioctylsulfosuccinat American Cyanamid Morwet® EFW Dispergiermittel-Blend Witco Corp. Pluronic® PE 6800 EO/PO-Blockcopolymer BASF AG Plurafac® LF 700 alkyliertes EO/PO-Blockcopolymer BASF AG SU-1 Verb. 47 aus Tabelle 1 Clefoxydim 2-{1-[2-(4-Chlorphenoxy)-propyloxyamino]-butyl}-5-tetrahydrothiopyran-3-yl-cyclohexan-1,3-dion Cinidon-ethyl Ethyl-(Z)-2-chlor-3-[2-chlor-5-(4,5,6,7-tetrahydro-1,3-dioxoisoindoldion-2-yl-)-phenyl)acrylat The table below explains the components used in the examples: Surname chem. description source Tamol® NH Naphthalene sulfonic acid-formaldehyde condensate BASF AG Ufoxane® 3A Na ligninsulfonate Borregaard Extrusil® highly disperse calcium silicate Degussa Sipernat® 22 finely divided silica Degussa SRE antifoam Silicone oil emulsion Wacker-Chemie Lutensol® ON 60 Fatty alcohol ethoxylate (6EO) BASF AG Lutensol® ON 80 Fatty alcohol ethoxylate (8EO) BASF AG Aerosol® OT-B dioctylsulfosuccinate American cyanamide Morwet® EFW Dispersant blend Witco Corp. Pluronic® PE 6800 EO / PO block copolymer BASF AG Plurafac® LF 700 alkylated EO / PO block copolymer BASF AG SU-1 Verb. 47 from Table 1 clefoxydim 2- {1- [2- (4-chlorophenoxy) -propyloxyamino] -butyl} -5-tetrahydrothiopyran-3-yl-cyclohexane-1,3-dione Cinidon-ethyl Ethyl (Z) -2-chloro-3- [2-chloro-5- (4,5,6,7-tetrahydro-1,3-dioxoisoindoldion-2-yl -) - phenyl) acrylate

    PrüfmethodenTest Methods

    Der Wirkstoffgehalt an SU der Formulierungen gemäß den vorstehenden Beispielen wurde jeweils mittels quantitativer HPLC bestimmt, und wird in Tabelle 3 in Prozent angegeben.The active ingredient content of SU of the formulations according to the above Examples were determined using quantitative HPLC, and is given in Table 3 in percent.

    Versuche zur Lagerstabilität :Storage stability tests:

    Zur Untersuchung der Lagerstabilität wurden Proben der jeweiligen Formulierung gemäß dem Beispiel 1 und den Vergleichsbeispielen 1 bis 3 für eine bestimmte Zeit (14 d oder 30 d) in fest verschlossenem Glasgefäßen bei der jeweils angegebenen Temperatur (54 °C bzw. 50 °C) gelagert. Anschließend werden die Proben untersucht und mit dem Vergleichswert zu Beginn der Lagerung (Nullwert) verglichen. Der Wirkstoffgehalt wird als relativer Anteil des SU, bezogen auf den Nullwert (in Prozent) angegeben.Die Lagerversuche wurden in Anlehnung an die Methode CIPAC MT 46 durchgeführt. Dabei wird die Langzeitstabilität eines Produkts durch Kurzlagerung bei erhöhter Temperatur abgeschätzt.Samples of the respective Formulation according to example 1 and the comparative examples 1 to 3 for a certain time (14 d or 30 d) in fixed sealed glass jars at the specified temperature (54 ° C or 50 ° C) stored. The samples are then examined and with the comparison value at the beginning of storage (zero value) compared. The drug content is called a relative proportion of the SU, based on the zero value (in percent) Storage tests were carried out based on the CIPAC MT 46 method carried out. The long-term stability of a product estimated by short storage at elevated temperature.

    Tabelle 3 gibt die Ergebnisse aus der Bestimmung der Lagerstabilität der hergestellten festen Mischungen aus dem Beispiel 1 und den Vergleichsbeispielen 1-3 wieder. Bsp.- Nr. Adjuvans Wirkstoffgehalt in Gew.% rel. Wirkstoffgehalt SU nach 14 d, 54°C V1 Lutensol®ON 80 3,2 16 V2 Lutensol ON 60® 3,2 14 V3 Pluronic®PE 6800 3,7 3 1 Plurafac® LF 700 5,5 83 Table 3 shows the results from the determination of the storage stability of the solid mixtures prepared from Example 1 and Comparative Examples 1-3. Example no. adjuvant Active substance content in% by weight rel. Active substance content SU after 14 d, 54 ° C V1 Lutensol®ON 80 3.2 16 V2 Lutensol ON 60® 3.2 14 V3 Pluronic®PE 6800 3.7 3 1 Plurafac® LF 700 5.5 83

    Die Ergebnisse zeigen die überlegenen Eigenschaften der erfindungsgemäßen festen Mischungen.The results show the superior properties of the invention solid mixtures.

    Claims (7)

    1. A solid mixture comprising
      a) an active ingredient from the group of the sulfonylureas and
      b) an alkyl ether of a copolymer of C2-C4-alkylene oxides.
    2. A solid mixture as claimed in claim 1, comprising a sulfonylurea of the formula I
      Figure 00290001
      where the substituents have the following meanings:
      R1
      is C1-C4-alkyl which can have attached to it one to five of the following groups: methoxy, ethoxy, SO2CH3, cyano, chlorine, fluorine, SCH3, S(O)CH3;
      halogen;
      a group ER19 where E is O, S or NR20;
      COOR12;
      NO2;
      S(O)nR17, SO2NR15R16, CONR13R14;
      R2
      is hydrogen, methyl, halogen, methoxy, nitro, cyano, trifluoromethyl, trifluoromethoxy, difluoromethoxy or methylthio,
      Y
      is F, CF3, CF2Cl, CF2H, OCF3, OCF2Cl, C1-C4-alkyl or C1-C4-alkoxy;
      X
      is C1-C2-alkoxy, C1-C2-alkyl, C1-C2-alkylthio, C1-C2-alkylamino, di-C1-C2-alkylamino, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy,
      R
      is hydrogen or methyl;
      R19
      is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl or C3-C6-cycloalkyl, each of which can have attached to it 1 to 5 halogen atoms. In the event that E is O or NR20, R19 is furthermore also methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonyl or dimethylsulfamoyl;
      R20
      is hydrogen, methyl or ethyl;
      R12
      is a C1-C4-alkyl group which can have attached to it up to three of the following radicals: halogen, C1-C4-alkoxy, allyl or propargyl;
      R17
      is a C1-C4-alkyl group which can have attached to it one to three of the following radicals: halogen, C1-C4-alkoxy, allyl or propargyl;
      R15
      is hydrogen, a C1-C2-alkoxy group or a C1-C4-alkyl group;
      R16
      is hydrogen or a C1-C4-alkyl group,
      n
      is 1 - 2
      Z
      is N, CH.
    3. A solid mixture as claimed in claim 1 or 2, comprising a further herbicidally active ingredient c).
    4. A solid mixture as claimed in any of claims 1 to 3, comprising 0.5 to 75 % by weight of component a).
    5. A solid mixture as claimed in any of claims 1 to 4, comprising 1 to 50 % by weight of component b).
    6. A method of controlling undesirable vegetation, which comprises treating the plants and/or the area to be kept free from the plants with a herbicidally active amount of a solid mixture as claimed in claim 1.
    7. A process for the preparation of herbicidal formulations, which comprises mixing a sulfonylurea with an alkyl ether of a copolymer of C2-C4-alkylene oxides.
    EP98922619A 1997-03-24 1998-03-12 Solid mixtures based sulfonylurea and adjuvants Expired - Lifetime EP0971590B1 (en)

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    DE102005037336A1 (en) * 2005-08-04 2007-02-08 Degussa Ag Carbon material
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    WO1998042192A1 (en) 1998-10-01
    HUP0001516A3 (en) 2001-08-28
    ES2201491T3 (en) 2004-03-16
    AR012155A1 (en) 2000-09-27
    TW453856B (en) 2001-09-11
    EP0971590A1 (en) 2000-01-19
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